KR102094604B1 - Fire Resistant Resin - Google Patents

Abstract

The present disclosure relates to a fire retardant composition. The fire retardant resin composition comprises 10 to 30% by weight of metal hydroxide, 10 to 20% by weight of phosphate, 3 to 8% by weight of boron compound, 1 to 10% by weight of alum, 5 to 10% by weight of polymerizable acrylic monomer, and 20 to 50% by weight of water. It may include.

Description

Fire Resistant Resin Composition

The present invention relates to a firestop resin composition. More specifically, it relates to a composition of a fire-resistant resin injected between glass sheets in a fire-resistant glass of a laminated structure.

In general, fireproof glass has a laminated structure composed of two or more sheets of glass, and a method of injecting firestop resin between glass sheets is used. When the fireproof glass is installed on the fire door, the fire resistant glass needs to satisfy the fire door performance, and thus, improved fire performance is required compared to the fire glass installed elsewhere.

According to Article 26 of the Rules for Standards for Evacuation and Fire Protection of Buildings, the first class fire doors must secure fire protection performance of at least 30 minutes according to the national industry standard KS F 2268-1. Fire resistance refers to the ability to inhibit heat transfer to the back side during the specified time period of a standard fire test where one side is exposed to fire. According to the national industry standard KS F 2268-1, the average of the temperatures measured at five locations in the fire door should not rise above 140K above the initial temperature. Here, the initial temperature refers to the average temperature of the non-heated surface at the start of the test. In addition, the temperature measured in all thermocouples should not rise above 180K above the initial temperature.

When fireproof glass is exposed to a fire, the glass sheet directly exposed to the fire bursts. As a result, the firestop resin injected between the glass sheets is directly exposed to the fire. In this case, the firestop resin provides a thermal barrier together with the inner glass sheet that has not yet ruptured to prevent the spread of flame and smoke. However, the firestop resin used in the existing firestop glass does not have high firestop performance, and thus cannot effectively prevent the spread of flame and smoke. In addition, the fire performance of fire doors required by related laws and regulations is not satisfied.

On the other hand, in general, the firestop resin used to manufacture fireproof glass is injected into an empty space called a cell formed between the fireproof glass, and this manufacturing method is called a cast-in-place method. However, when the resin is injected in this manner, the control of the resin is difficult due to excessive fluidity of the resin, resulting in air bubbles or a problem that the optical transparency of the firestop resin is deteriorated, such as accumulation of firestop resin on the floor.

In addition, the existing firestop resin also has a problem of deteriorating transparency due to a haze phenomenon. When light passes through the firestop resin, depending on the type of material, in addition to reflection or absorption, light is diffused due to the intrinsic properties of the material, resulting in an opaque cloudy appearance, which is called a haze phenomenon. When the haze phenomenon is severe, it is difficult to secure the transparency of the firestop resin to a desired level, and there is also a problem that it is difficult to use it in the fireproof glass for construction, which values aesthetic value.

The present disclosure provides a composition for solving the above problems of the firestop resin.

An object of the present invention is to provide a firestop resin having improved firestop performance.

In addition, an object of the present invention is to provide a fire resistant resin having a high viscosity (ie, low fluidity) by reducing the amount of water mixed with the fire resistant resin.

In addition, another object of the present invention is to provide a firestop resin that reduces haze and improves transparency.

In addition, another object of the present invention is to facilitate the manufacturing process of the laminated fireproof glass into which the firestop resin is injected.

The firestop resin composition according to the present disclosure includes: 10-30% by weight of metal hydroxide, 10-20% by weight of phosphate, 3-8% by weight of boron compound, 1-10% by weight of alum, 5-10% by weight of polymerizable acrylic monomer and water It may contain 20 to 50% by weight.

The laminated fireproof glass according to the present disclosure may include the fireproof resin composition according to the present disclosure.

The firestop resin composition according to an embodiment of the present disclosure is prepared by mixing a metal hydroxide, boron compound, phosphate and alum in an optimal capacity, and has transparency in normal use, yet effectively forms and protects a carbonized film in the event of a fire, and has a remarkable firestop performance. Improved. Particularly, when the fire-resistance resin is injected between the glass sheets of the laminated fire-resistant glass, the fire-resistant performance of the laminated fire-resistant glass is significantly increased since the carbonized film formed in the event of a fire is tightly bonded to the glass sheet of the fire-resistant glass.

In addition, the firestop resin composition according to an embodiment of the present disclosure is prepared by mixing a metal hydroxide, a boron compound, a phosphate and alum in an optimal capacity, thereby significantly reducing the amount of water used in manufacturing the resin and increasing the viscosity of the resin. As a result, the manufacturing process has been facilitated and haze can be significantly reduced.

The effects of the present disclosure are not limited to the effects mentioned above, and other effects not mentioned will become apparent to those skilled in the art from the description of the claims.

1 is a cross-sectional view of a laminated fireproof glass according to an embodiment of the present invention.

The present invention, metal hydroxide 10 to 30% by weight, phosphate 10 to 20% by weight, boron compound 3 to 8% by weight, alum 1 to 10% by weight, polymerizable acrylic monomer 5 to 10% by weight and water 20 to 50% by weight It provides a firestop resin composition comprising a. The fire retardant composition may additionally contain 0.02 to 0.05 moles of a crosslinking agent compared to 1 mole of a polymerizable acrylic monomer, and may also contain at least 0.5% by weight of a cryoprotectant to prevent freezing. In addition, the firestop resin composition may contain a polymerization initiator 0.01 to 1% by weight.

The present invention provides a laminated fireproof glass comprising a firestop resin according to an embodiment of the present disclosure. In the laminated fireproof glass according to the present invention, as shown in FIG. 1, a plurality of glass sheets 110 and 120 are stacked through a spacer 150 to be spaced apart at predetermined intervals, and the firestop resin 130 is spaced apart. It is composed by injection. The laminated glass sheet and the firestop resin may be closed by the frame 140.

Metal hydroxide

The firestop resin according to the present invention includes 10 to 30 wt% of metal hydroxide compared to 100 wt% of the firestop resin composition.

In one embodiment, the metal hydroxide may be selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, potassium hydroxide, and sodium hydroxide, and preferably magnesium hydroxide. Aluminum hydroxide and magnesium hydroxide may be selected as materials having excellent fire-resistance performance and environmental advantages. In the case of selecting magnesium hydroxide, charcoal (charred layer) is formed as heat is applied to magnesium hydroxide, and thus has a function of improving heat shielding properties. The carbonized film formed on the firestop resin is effective in blocking radiant heat.

The metal hydroxide is preferably 10 to 30% by weight compared to 100% by weight of the firestop resin composition. When the metal hydroxide content is less than 10% by weight, the fire-retardant performance decreases, and when it exceeds 30% by weight, the weight of the resin itself becomes too large, and it is difficult to expect further fire-retardant effects.

According to the present invention, as a flame retardant, as well as a metal hydroxide, a phosphate, a boron compound, and alum are additionally used, so that the weight percent of the metal hydroxide can be reduced, thereby reducing the weight of the resin itself and improving the fire retardant performance and transparency of the fire resistant resin. Can be improved.

phosphate

The firestop resin according to the present invention contains 10 to 20 wt% of phosphate relative to 100 wt% of the firestop resin composition.

In one embodiment, the phosphate may include zinc, aluminum, magnesium, tin, titanium or calcium added metal phosphate. In another embodiment, the phosphate salt may be a mixed metal phosphate salt. The additional metal may be an alkali metal such as lithium or potassium, which serves to lower the temperature at which the phosphate melts and coats the firestop resin. As another additional metal, it may be a multivalent metal such as aluminum, calcium, or magnesium, which serves to increase the viscosity of the firestop resin. Since the firestop resin is injected into the space between the glass sheets, when the viscosity is low, a phenomenon occurs that accumulates at the bottom of the cell. In order to prevent such a phenomenon, a high viscosity is required. When using a phosphate to which a polyvalent metal such as aluminum, calcium or magnesium is added, a high viscosity fireproof resin can be produced.

As another embodiment, the additional metal may be chloride, and the metal phosphate may form chlorophosphate.

Phosphate, when used with metal hydroxides, can significantly improve the fire retardant performance of fire retardant resins. The principle is as follows.

When the fireproof resin composition containing the metal hydroxide is burned by heat or flame, a charred layer is formed. That is, during the combustion process, a carbonization reaction occurs on the surface of the firestop resin to form a carbonized film. The carbonized film acts as a heat barrier to block flame or heat, hindering heat transfer to the inside, and delaying or hindering thermal decomposition to the inside. Phosphate serves to protect the carbonized film.

The process in which the fireproof glass (100, hereinafter, refer to FIG. 1) and the firestop resin 130 injected therein is burned by fire is as follows. The first glass sheet 110, which comes into direct contact with the fire, collapses and breaks down because the glass sheet has been exposed to a lot of heat in a short time. Then, the firestop resin 130 injected between the glass sheets is exposed to the outside. The exposed firestop resin 130 is gradually burned down and burned by heat, so that only the thickness is reduced in a state of maintaining the char formation. As high temperature heat is continuously applied, the firestop resin 130 remains in the form of ash to form a constant carbonized film. The carbonized film is attached to the second glass sheet 120 disposed further inside, and the carbonized film serves to block the second glass from directly contacting heat or flame. If all of the exposed firestop resin 130 is lost during the combustion process or the carbonized film is too thin, the second glass sheet 120 is directly exposed to heat or flame, and like the first glass sheet 110, it breaks and collapses. . In this case, since there is no barrier to block heat, the heat from the fire is transferred to the inside and the temperature of the other side of the heating rises.

As described above, it is important to protect the carbonized film in order to improve the fire resistant performance of the fire resistant resin, and phosphate serves to protect the carbonized film. Phosphate flows over the carbonized film generated in the event of a fire to protect the carbonized film. The higher the concentration of the phosphate solution, the higher the protective effect of the carbonized film, so that the overall fire resistance of the fire resistant resin is also improved.

On the other hand, phosphate serves not only as a flame retardant, but also as an auxiliary for controlling the reaction time and gel strength of the resin composition. When a certain amount of a polymerizable acrylic monomer and a crosslinking agent are used, properties such as an increase in gel strength are improved, but haze occurs inside the gel, causing visual deformation (ie, haze phenomenon). Since the chemical reaction of the resin composition is caused by heat, the temperature difference between the inside and the outside of the resin composition should be reduced, but it is very difficult to control. When phosphate is added to the resin composition, the phosphate delays the reaction time of the resin composition and serves to control the viscosity after the reaction of the resin composition, so that the process of manufacturing the resin can be more easily controlled. Therefore, the resin composition can be prepared so that there is no optical distortion phenomenon in which a haze or an object on the other side that is locally observed by the use of phosphate is distorted.

Phosphate is preferably 10 to 20% by weight compared to 100% by weight of the firestop resin composition. When the fire retardant resin composition contains less than 10% by weight of phosphate, the ability of the phosphate to protect the carbonized film is significantly reduced. When the fire retardant resin composition contains more than 20% by weight of phosphate, the content of the material for forming the carbonized film is relatively insufficient, thereby deteriorating the fire prevention performance of the entire fire retardant resin.

Boron compound

The firestop resin according to the present invention contains 3 to 8 wt% of a boron compound relative to 100 wt% of the firestop resin composition.

According to an embodiment, the boron compound may be solid boric acid (H ₃ BO ₃ ) having a purity of 99% or more having a trivalent functional group. According to another embodiment, the boron compound may be an boron acid anhydride which is an organic boron compound. An organic boron compound (organoboron compound) means a compound that contains boron and can be dissolved in an organic solvent and soluble in a resin. The organic boron compound may be sterically hindered boroester or sterically hindered boric anhydride. In particular, boron penetrates into the carbonized film formed in the event of a fire and bonds at a high temperature, thereby providing good mechanical stability to the carbonized film, thereby preventing oxidation and collapse of the carbonized film. Furthermore, in the event of a fire, the organic boron compound is converted to an inorganic borate, thereby improving adhesion between the carbonized film and the glass sheet surface.

When the boron compound is used, transparency is excellent, haze can be prevented, and the fluidity of the resin composition can be controlled. In addition, when a fire occurs, the boron compound is combined with a carbonized film to form a uniform and fine additional thermal barrier. In addition, when a fire occurs, the boron compound improves the adhesion between the carbonized film and the glass sheet, thereby preventing cracking, and consequently, improving the fire resistance performance of the fire resistant resin composition.

When the boron compound is used together with the phosphate salt, the carbonized film formed in the event of a fire can be more effectively protected as compared with the case where only the boron compound or the phosphate salt is used, and as a result, the fire protection performance of the firestop resin can be significantly increased. Furthermore, when the boron compound is used together with the phosphate salt, the amount of water used in resin production can be significantly reduced compared to when only the boron compound or phosphate salt is used. It can be easily controlled. In addition, the high viscosity of the firestop resin is effective in reducing the haze phenomenon.

When the mixed amount of boron compound is less than 3% by weight, the high temperature fluidity increases, and the resin is foamed during the fire test to prevent thermal blockage. There is a problem of breaking, and when it exceeds 8% by weight, there is a problem that cloudiness occurs.

alum

The firestop resin according to the present invention contains 1-10 wt% of alum compared to 100 wt% of the firestop resin composition.

According to one embodiment, the alum is preferably thallium-chromium-selenium alumina, ammonium alum, ammonium-iron alum, rubidium-cobalt alum or potassium aluminum sulfate, more preferably, the alum is aluminum potassium alum.

Alum has the general formula of MIAl (SO ₄ ) ₂ · 12H ₂ O or MI ₂ SO ₄ · Al ₂ (SO ₄ ) ₃ · 24H ₂ O. MI refers to a monovalent metal ion or other cation. Potassium alum (KAl (SO ₄ ) ₂ · 12H ₂ O) when the monovalent metal ion contained is potassium, and ammonium alum ((NH ₄ ) Al (SO ₄ ) ₂ · 12H ₂ when the cation is an ammonium ion O).

In addition, when other trivalent metal ions such as Ti, V, Cr, Mn, Fe, Co, Rn, Ru, Ir, Ga, In, Ta, Se, etc. are substituted for aluminum, it is also called alum in the broad sense. Named according to each metal ion, for example, (NH ₄ ) Fe (SO ₄ ) ₂ · 12H ₂ O is referred to as ammonium-iron alumina.

According to one embodiment, alum is used in an amount of 1 to 10% by weight compared to 100% by weight of a fire retardant resin composition. Fire resistance performance decreases when less than 1% by weight is used, and transparency decreases when more than 10% by weight is used. The use of alum in the firestop resin increases solids content, improves the molar ratio of hydroxide, and alum prevents heat while forming a foam layer behind the carbonized film. Preferably, the alum is potassium aluminum sulfate, because the transparency is improved when using other alum.

When alum is used together with boron compounds and phosphates, the carbonized film formed in the event of a fire can be most effectively protected compared to other examples, and as a result, the fire resistance of the fire resistant resin can be significantly increased.

water

The firestop resin according to the present invention contains 20-50 wt% of water compared to 100 wt% of the firestop resin composition.

When using unrefined water (e.g., tap water), it is difficult to color or degrade the transparency of the glass because chlorine ions and various alkali metal ions contained in the water form a complex with a metal hydroxide. desirable.

Polymerizable acrylic monomer and others

The firestop resin according to the present invention contains 5 to 10 wt% of a polymerizable acrylic monomer relative to 100 wt% of the firestop resin composition.

According to one embodiment, the polymerizable acrylic monomer is at least one member from the group consisting of acryl amide, methacryl amide, N-methyl acryl amide, N-methylol acryl amide, diacetone acryl amide and N-isobutoxymethyl acryl amide. Can be selected. Preferably, the polymerizable acrylic monomer is acryl amide. Acrylamide is easily compatible with phosphate solutions.

The polymerizable acrylic monomer is preferably used in an amount of 5 to 10% by weight compared to 100% by weight of the firestop resin composition. When it is used less than 5% by weight, the strength with the resin is low, so the adhesion with the glass is lowered.

The fire retardant composition according to the present invention may include a crosslinking agent for gelation of the resin and a cryoprotectant for preventing freezing. Crosslinking agents include N, N-methylenebis acrylamide, N, N-bis-acryl cystamine, ethylene diacrylate, dimethylaminopropionitrile and triethanolamine One or more types may be selected from the group consisting of, and may be used in an amount of 0.02 to 0.05 moles compared to 1 mole of the polymerizable acrylic monomer.

Anti-freezing agent may be selected from one or more of the group consisting of glycerin, ethylene glycol, triethanol amine and diethanolamine. Anti-freezing agents maintain transparency by preventing freezing of the fire-resistant resin layer when the outside temperature decreases after the fire-resistant glass is installed. That is, it is used to increase the freezing stability at low temperatures. The anti-freezing agent is preferably used in an amount of 0.5 to 10% by weight compared to 100% by weight of the fire-resining resin composition, and when used at less than 0.5% by weight, stability at low temperature is lowered. Falls.

The firestop resin according to the present invention may include a polymerization initiator. The polymerization initiator serves to polymerize the firestop resin. It is used in the range of 0.01 to 1.0% by weight compared to 100% by weight of the fire retardant resin composition, and can be selected from sodium persulfate or ammonium persulfate, and when ammonium persulfate is selected, the time for curing the resin may be shorter than other polymerization initiators.

Example

40 ~ 70 by mixing 20% by weight of metal hydroxide, 5% by weight of potassium aluminum sulfate, 10% by weight of polymerizable acrylic monomer, 0.1% by weight of trimethanolamine, 20% by weight of purified water, 20% by weight of phosphate, and 6% by weight of boron compound After heating to ℃ ℃ and stirred for 1.5 to 2 hours. A firestop resin composition is prepared by adding a polymerization initiator. Then, the fire retardant resin composition is injected into a thickness of 5 to 25 mm into each space between 2 to 5 3 to 10 mm transparent plate glass. The injected firestop resin composition is sealed with silicone or a hot melt adhesive. After that, it is allowed to stand for 40-60 hours at room temperature.

Comparative example

20% by weight of metal hydroxide, 5% by weight of aluminum sulfate potassium aluminate, 10% by weight of polymerizable acrylic monomer, 0.1% by weight of trimethanolamine, and 50% by weight of purified water, heated to 70 ° C and stirred for 1.5-2 hours. After preparing the mixed solution, a polymerization initiator is added to prepare a firestop resin composition. Then, the fire retardant resin composition is injected into a thickness of 5 to 25 mm into each space between 2 to 5 3 to 10 mm transparent plate glass. The injected firestop resin composition is sealed with silicone or a hot melt adhesive. After that, it is allowed to stand for 40-60 hours at room temperature.

Fire test

The fire test was conducted according to the IMO res A.754 (18): 1993 test method, and the test time standard was 60 minutes. The criteria for evaluating heat shielding are the average rise temperature on the back side and the maximum rise temperature on the back side. The average rise temperature should not exceed 140 ℃, and the maximum rise temperature should not exceed 180 ℃. Each test was run for 60 minutes. The example was not abnormal, and in the comparative example, the maximum temperature exceeded 180 ° C after 45 minutes.

The physical property evaluation was conducted in accordance with ISO12543-4 (Glass in building -Laminated glass and laminated safety glass), and a high temperature test and a humidity test were performed. The size of the specimen was 300 mm Х 300 mm. In the high temperature test, the fireproof glass structure was left at 100 ° C. for 2 hours, and then cooled at room temperature to observe changes in the appearance of bubbles, layer separation, and cloudiness. In the humidity test, after standing at 50 ° C and 80% for 14 days, the change in appearance for air bubbles, layer separation, and clouding was observed. The resistance at high temperature and humidity was observed through the physical property test, and the test results were good in the examples. On the other hand, in the comparative example, a haze phenomenon occurred at a high temperature.

division Example Comparative example Fire protection performance 60 minutes or more 45 minutes Average surface temperature ℃ (Standard: 140 ℃ or less) 90 ℃ 135 ℃ Maximum surface temperature ℃ (Standard: 180 ℃ or less) 119 ℃ 215 ℃ Appearance and property evaluation Good Haze phenomenon

The preceding description of the present disclosure is provided to enable those skilled in the art to make or use the present disclosure. Various modifications of the present disclosure will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to various modifications without departing from the spirit or scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited to the examples described herein, but is intended to be given the broadest scope consistent with the principles and novel features disclosed herein.

110, 120: glass sheet
130: firestop resin
140: frame
150: spacer

Claims (7)

A laminated fireproof glass comprising a plurality of glass sheets,
Fireproof resin composition injected between the glass sheet,
The firestop resin composition,
Metal hydroxide 10 to 30% by weight;
10-20% by weight of phosphate;
Boron compound 3-8% by weight;
Alum 1-10% by weight;
5 to 10% by weight of a polymerizable acrylic monomer; And
20-50% by weight of water
Including,
The phosphate is a mixed metal phosphate containing alkali metal, laminated fireproof glass. delete According to claim 1,
The boron compound is a dissolving solid boric acid, or an organic boron compound, laminated fireproof glass. According to claim 3,
The metal hydroxide is one or more selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium hydroxide, potassium hydroxide and sodium hydroxide, laminated fireproof glass. According to claim 4,
The alum is one or more selected from the group consisting of thallium-chromium-selenium alumina, ammonium alumina, ammonium-iron alumina, rubidium-cobalt alumina, or potassium aluminum sulfate. According to claim 1,
The polymerizable acrylic monomer is characterized in that the acrylic amide, laminated fireproof glass. delete

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